Stabilized opaque detergent composition



United States Patent Office 3,382,177 STAEELHZED (EPAQUE DETERGENTCGMPOSlTlflN Douglas Woodrutf, Marengo, ill, assignor to MortonInternational, line, a corporation of Delaware No Drawing. Originaiappiication Dec. 11, 1963, Ser. No.

329,873. Divided and this appiication Mar. 9, 1967,

Ser. No. sssgso 3 (Ziaixns. (Cl. Z5289) This invention is a division ofmy application Ser. No. 329,873, filed Dec. 11, 1963, now Patent No.3,340,217 and relates to the production of novel cross-linked polymericlatices of the type useful in opacifying aqueous liquid detergentcompositions, to opacified detergent compositions made therefrom, and tothe process of opacifying aqueous liquid detergent compositions.

An aqueous liquid deter ent composition, as the term is used herein, isone containing water, a surface active agent and optionally one or moreof the following ingredients: a foam stabilizer, a foam booster, a smallamount of a hydrotrope, e.g. an alcohol. Usually the whole compositionis adjusted to a neutral pH. The above type composition is oftencharacterized as a light-duty liquid detergent. A socalledgeneral-purpose or a heavy-duty liquid detergent may contain, inaddition, one or more of the so-called alkaline boosters, such as alkalimetal silicates, carbonates, polyphosphates and the like.

Aqueous liquid detergents are used extensively in dish washing,laundering, bathing, and in general purpose cleaning preparations. Theyfrequently contain solubilizing aids (hydrotropes) such as sodiumbenzene sulfonate, sodium toluene sulfonate, sodium Xylene sulfonateand/ or alcohol. They are usually clear in appearance and have varyingdegrees of viscosity.

Dyes and particularly opacifying agents are conventionally added tothese products to improve their attractiveness to consumers, who,through long exposure to cosmetic products in the form of creams andlotions, have come to associate a creamy or opaque, milky appearancewith mildness, softness and luxuriousness.

Polymer latices of varying descriptions have heretofore been used toopacify detergent formulations. However, many liquid detergents whichare opacified with conventional polymer latices, particularly thosecontaining alcohols, display poor storage stability and often soondeposit a sludge-like material which destroys the attractiveness of theproduct and thereby defeats the original objective.

It would, therefore, be desirable to provide improved polymer laticeswhich have utility in the production of stable, opacified liquiddetergent compositions.

Accordingly, one object of this invention is the provision of polymerlatices for use in opacifying liquid detergent compositions.

Another object of this invention is the provision of a novel improvedprocess for producing improved opacifier latices.

A further object is the provision of stable, opacified liquid detergentscontaining various concentrations of alcohol.

3,382,177 Patented May 7, 1968 Another object of this invention is theprovision of polymer latices which are useful in opacifying liquiddetergent compositions containing a hydrotrope.

Still another object is the provision of polymer latices for use inopacifying commercial cleaning and bleaching preparations such as toiletbowl cleaners, liquid laundry bleaches and household ammonia.

A still further object of this invention is the provision of a processfor opacifying liquid detergent compositions.

The fulfillment of these and other objects of the present invention maybe better understood by reference to the following specification andappended claims.

Accordingly, in one broad form, the present invention comprises aninterpolymer latex, said interpolymer containing in cross-linkedpolymerized form a major proportion of a monomer selected from the groupconsisting of styrene and methylated styrene and a minor proportion ofan unsaturated acid, a hydrophilic monomer and up to 2 parts of divinylbenzene per parts of total monomer. More particularly the interpolymercomprises from about 78 to 96 parts by weight of a monomer selected fromthe group of styrene and methylated styrenes, from about 1 to 20 partsby weight of an unsaturated acid selected from the group of methacrylicacid, acrylic acid and itaconic acid, and from 1 to 20 parts by Weightof a hydrophilic monomer selected from the group consisting of glycidylinethacrylate, and glycidyl acrylate, and up to about 2 parts by weightof divinylbenzene, the proportions of said monomers being selected tototal 100 parts.

Another broad form of the present invention is a process for producingthe herein above described cross-linked interpolymer latex whichpreferably comprises carrying out said polymerization by dividing saidmonomers into two fractions wherein the first contains a majorproportion of the monomer of the group consisting of styrene andmethylated styrene, a major proportion of the unsaturated acid monomerand all of the divinyl benzene monomer, said first fraction being addedas a first monomer phase to an aqueous polymerization medium containinga surface active agent and a free radical catalyst and upon completionof the addition of the said first monomer fraction, adding a secondmonomer fraction, containing the hydrophilic monomer and the remainingportion of monomers.

The interpolymer latex product preferably has a solids content of fromaboutSO to 50 percent by weight on a total latex basis.

Another form of the present invention is a stable opacified aqueousliquid detergent composition containing a detergent selected from thegroup consisting of anionic and nonionic surface active agents and anopacifying latex as above defined. Of particular interest are detergentcompositions which contain alcohols as solubilizing aids and/orhydrotropes. The term detergent or surface active agent also includesspecific surface active agents which are known to the art as foamboosters and/or foam stabilizers for their particular function in thedetergent formulation. Preferably the opacifier is present (on a solidsbasis) in amounts of from 0.2 to 14 parts per 100 parts of surfaceactive agent. The alcohol is preferably present in amounts of from 3.6to 83 parts on the same basis, and when present the hydrotrope, otherthan alcohol, preferably in amounts of from 1.8 to 83 parts.

Expressed as percentages, one specific group of detergent formulationsmay contain the following:

Percent (by weight) Surface active agent (including detergent, foambooster and/or foam stabilizer) 18-55 Alcohol 2-15 Hydrotrope (otherthan alcohol) 1-15 Water 60-80 Opacifier latex-solids (30-50% solids) .1

Anionic and nonionic surface active agents utilized in the opacifiedliquid detergents of the present invention include sodiumdodoceylbenzene sulfonate, alkali salts of complex organic phosphateesters, alkyl aryl sulfonates, sodium lauryl ether sulfates, sodiumlauryl sulfate, the octyl nonyl phenoxy (polyethyleneoxy)ethanols,polyoxyalkylene ethanols, polyoxyethylene sorbitan fatty acids and fattyacid alkanolamides, and the like.

Although, as previously pointed out, the latices herein described areparticularly useful in opacifying liquid detergents containing alcohol,it should be noted that they are also effective in opacifying light dutyliquid detergents, heavy duty liquid detergents, shampoos, hair-wavingsolutions, liquid toilet bowl cleaners, laundry bleaching liquids andhousehold ammonia, which compositions conventionally contain materialswhich adversely affect the stability of ordinary opacifying latices.

In the interpolymer latex compositions of the present invention themonomers may be present in varying amounts. In the preferred aspects ofthis invention, monomers of the group of styrene and methylated styreneare present in amounts of from about 85 to 95 parts by weight per 100parts of total monomer and most preferably from 87 to 93 parts by weighton the same basis. Of the aforesaid monomers, styrene is preferred.Exemplary 0f the methylated styrene monomers useful in preparing theinterpolyrner latices of the present invention are monomethyl styrenes,such as 4-rnethyl styrene, and dimethyl styrenes, such as 2,4-dimethylstyrene. It should be understood that mixtures of styrene and/ ormethylated styrenes can also be used.

The unsaturated monomeric acids such as methacrylic acid, acrylic acidand itaconic acid may be used interchangeably in preparing theinterpolymer latex compositions of the present invention. In addition toforming an essential component of the interpolymer latices of thisinvention, the unsaturated acids also function to impart freeze-thaw andmechanical stability to the resultant latex. In the most preferredembodiment of the present invention they are used in proportions of from1 to parts by weight on a 100 parts of total monomer basis.

Glycidyl methacrylate or glycidyl acrylate is a hydrophilic monomerwhich is essential to the successful operability of the latices of thepresent invention, and each may be used interchangeably in thepolymerization process. It is preferred to use from 2 to 10 parts byweight on a 100 part of total monomer basis.

Divinylbenzene is a cross-linking agent which in the proportions usedimparts stability to the resultant latex.

The cross-linked character of the latices of the present invention isattested to by the fact that upon drying at room temperature, there isobtained a particulate solid which is insoluble in acetone, methyl ethylketone, toluene, dimethylformamide and benzene. The latices of thepresent invention are non-film forming, and preferably have an averageparticle size of less than 0.5 micron. The amount of diminylbenzene usedis critical and should not exceed approximately 2 parts by weight per100 parts of total monomers. In the present compositions, divinylbenzenein excess of about 2 parts by Weight tends to reverse the stabilitywhich lesser amounts impart and induces coagulation of the latex. Thedivinylbenzene used herein is a technical grade in the form of a 55percent active solution containing 45 percent of ethyl vinylbenzene.Ethyl vinylbenzene has of course no functional capability ofcross-linking.

The latices of the present invention are further characterized by theirunusual stability to coagulation or pre cipitation by methanol, theusual polymer emulsion precipitating agent, or by dilute aqueoussolutions of hydrochloric acid. It is believed that this stability isthe result of a combination of attributes such as the cross-linkedcondition of the eopolymers comprising the latices, coupled with theeffect of the hydrophilic monomers, glycidyl methacrylate or glycidylacrylate.

Exemplary of the alkaline materials which are satisfactory in the pHadjustment of the present latices are the following: lvlonoethanolamine,diethanolamine, triethanolamine, ammonium hydroxide, sodium hydroxide,monoisopropanola'mine, diisopropanolarnine, triisopropanolamine,3-aminopropanol, morpholine and tetraethanol ammonium hydroxide. Thesealkaline materials are used to adjust the pH of the latex product tofrom about 7 to 11.

The type of surface active agents used in the polymerization procedureof the process of the present invention is not critical. Anionicsuriactants, exemplified by alkyl aryl suifonates and/or alkyl sulfates,may be used alon or in the blends with nonionic surfactants, in amountsranging from about 1 to 10 percent on a total monomer basis. The time ofpolymerization is likewise not critical and it should be understood thatby utilizing certain catalyst systems, such as, for example, redoxsystems, the polymerization may be carried out in a relatively shorttime. Accordingly, the time of polymerization may extend from about toabout 240 minutes, although for most purposes from about to 180 minutesare adequate.

The polymerization procedure of the present invention employed toprepare the herein described latices is an aqueous emulsionpolymerization technique utilizing free radical or peroxide typecatalysts. It is possible to prepare the present opacifier latices byeither a one or a two phase monomer addition procedure. However, a twophase monomer addition procedure is preferred, as it results in a latexwhich imparts greater storage stability to a liquid detergent in whichit is incorporated than does that produced by a one monomer phaseaddition.

In the most preferred process of the present invention, a two phasemonomer addition procedure is employed in which from 60 to 90 percent byweight of the total styrene or methylated styrene used, from 50 to 80percent by weight of the total unsaturated acid used, and 100 percent byweight of the total divinylbenzene used are added as a first monomerphase or fraction to a reaction vessel containing water, a surfaceactive agent, and a free radical catalyst. Upon completion of theaddition of the first monomer phase, a second monomer fraction or phasecontaining the balance, i.e. from 10 to percent by weight of the totalstyrene used, 20 to percent by weight of the total unsaturated acidused, and 100 percent by weight of the total hydrophilic monomer used,is added. The temperature is maintained at from to C. until completionof the monomer addition. Upon completion of the reaction, the pH isadjusted to from 7 to 11 as above indicated. It should be understoodthat the parts by weight or percentages referred to herein havereference to monomeric constituents only and do not include diluents,carriers, additives, or other material which may be used in conjunctionwith the monomers in the polymerization process.

In the preferred two-phase monomer addition procedure of the presentinvention, the divinylbenzene should be present in the first monomerfraction or phase which is added to the reaction vessel containingwater, a surface active agent, buffer and free radical catalyst. Ifdivinylbenzene is added as a component of the second monomer phase, theresultant latex exhibits unsatisfactory stability when incorporated in aliquid detergent composition.

For a more complete understanding of the present invention, reference isnow made to the following specific examples illustrating the preparationof the various operable copolymer latices, their evaluation asopacifiers for liquid detergent compositions containing variousconcentrations of alcohol, and opacified detergent compositions.

EXAMPLE 1 Parts by Parts by Weight Weight per 100 Parts Total MonomerKettle Charge:

Ammonium salt of sulfate ester of an alkylpllzenoxypoly(ethyleneoxy)- 15.3 parts active. 2 Active.

The kettle charge is added to a suitable vessel equipped with refluxcondenser, mechanical stirrer, addition funnel and thermometer.

The charge is heated to 90-92 C. with continuous stirring. When thecharge reaches this temperature, the catalyst premix is added withstirring. Upon completion of the addition of the catalyst premix,monomer Phase A is added to the stirred reaction medium at a uniformrate over a period of about 60 minutes. After the addition of monomerPhase A, the addition of monomer Phase B is begun at a constant rateover a period of about 30 minutes. The entire reaction is carried out attemperatures varying between 85 C. and 95 C. Stirring and heating atthis temperature is continued for about 60 minutes after the completionof the addition of monomer Phase B, after which the batch is neutralizedwith diethanolamine (neutralization charge) and heated at 90 C. for anadditional 30 minutes and then cooled to form the finished product. Thefinal product has a solids content of about 40%, an average particlesize of less than 0.5 microns and a pH of about 9.5.

Evaluation of opacifier stability To evaluate the stability of a typicalliquid detergent opacified with the composition of Example 1, thefollowing liquid detergent was employed in this as well as in testshereinafter described as representative of a typical aqueous light-dutyliquid detergent containing alcohol as the solubilizing aid.

Parts by Weight Nonyl phenoxy (polyethyleneoxy)ethanol (15 molesethylene oxide) 11.0

Lauric diethanolamide 5.0 Sodium alkyl aryl sulfonate (57.5% active)25.5

Ethyl alcohol 8.0 Water, ion exchanged 40.5 Dilute sulfuric acid toadjust to about pH 7.0.

One part by weight of opacifier latex prepared as described in Example 1is dispersed in parts by Weight of ion exchanged water. This entirelatex dispersion is then added to 90 parts by weight of the above liquiddetergent solution with efficient stirring. This produces a 6 stable,opaque, milky lotion-like liquid which is tested for stability bystorage at 125 F. There is no change in the appearance of the opacifieddetergent after more than 30 days storage at 125 F.

Example 1 was repeated except that the divinylbenzene component wasadded with the second or phase B component. The resultant latex whenformulated with the detergent composition described above showeddeterioration and loss of stability after two days accelerated storageat 125 F.

EXAMPLE 2 A copolyrner latex is prepared as set forth in Example 1 withthe exception that vinyl toluene (4-methyl styrene) is substituted forstyrene. When the resultant opacified detergent composition of Example 1is tested for stability by storage at 125 B, there is no change in theappearance of the opacified detergent after more than 30 days storage at125 F.

EXAMPLE 3 A copolymer latex is prepared as set forth in Example l withthe exception that in monomer Phase B, 30 parts of glycidyl acryla'te issubstituted for 30' parts of glycidyl methacrylate. When this opacifieddetergent composition is tested for stability by storage at =l25 F.,there is no change in the apparan-ce of the opacified detergent aftermore than 30 days.

EXAMPLE 4 A copolymer latex is prepared as in Example 1 except thatacrylic acid is substituted for methacrylic acid.

The opacified detergent composition of Example 1 using this latex isstable for 30 days at 125 F.

EXAMPLE 5 A copolymer latex is prepared as set forth in Example 1 withthe exception that in Monomer Phase B, 30 parts of styrene issubstituted for 30 parts of glycidyl methacrylate.

When this opacified detergent composition is tested for stability bystorage at 125 F, there is considerable separation in less than 24hours, as evidenced by a sludgelike layer on the bottom of the containerand a loss of opacity in the detergent.

EXAMPLES 6 to 11 TABLE I Examples 6 7 8 9 1O 11 Monomer Phase B:

Styrene 85 85 85 85 R5 Methacrylic Acid 5 5 5 5 5 5 Methyl Methacrylate.Cellosolve Acr at Acrylonitrile Ethyl Acrylat Hydroxyethyl MethacrylateGlycidyl Mcthacrylate Apperancc aiter storage at 1 Considerableseparation in less than 24 hours. 2 No change in appearrance after 30days.

The results of opacifier evaluations of the latices prepared accordingto Examples 6 through 11 illustrate the essentiality of glycidylimethacrylate or glycidyl acrylate to the preparation of interpolymerlatices which exhibit stability in opacifying aqueous liquid detergentcompositions having an appraciable alcohol content. Example 1 1demonstrates that increasing the glycidyl methacrylate content of thelatex does not impair its opacifyin-g capability.

EXAMPLE 12 An interpolymer latex is prepared as set forth in Example 1with the exception that the addition of diethanolamine is omitted. Theresultant pH is 5.7. When the detergent composition described in Example1 is opacified using the copolymer latex of Example 12 and is tested forstorage stability as before, there is a slight separation af-ter oneweek. The stability of the detergent opacified with the latex of Example12, when compared with the stability of the same detergent compositionopacified With the latex of Example 1, illustrates the additionalstability achieved by the regulation of the pH to from 7 to 11.

EXAMPLE 13 Percent by Parts by Weight Weight Monomer Basis KettleCharge: Water 815 Catalyst Premix:

Ammonia persullate 3.1 Water 15.0 Monomer Phase A:

Styrene 410 72. 4 Methacrylic acid 26 4. 6 Divinylbcnzene (55% a 1 l 21.0 Ammonium salt of sulfate ester of an alkylphenoxypoly(ethyleneoxy)ethanol (58% active) 22.8 Monomer Phase B:

Styrene 92 16. 1 Methaerylic acid 18 3.1 Glyeidyl mcthacryla 16. 4 2. 9Neutralization Charge:

Aqueous solution of sodium hydroxide 1 5.5 parts active. 1 Active.

The procedure followed in the preparation of the latex of Example 13 isthat set forth in Example 1.

The resultant opacified detergent containing 1% by weight of the latexof Example 13 is stable for more than 30 days upon storage at 125 F.

EXAMPLE I14 Parts by Parts by Weight per Weight 100 Parts Total MonomerKettle Charge:

Ammonium salt of sulfate ester of analkylphcnoxy-poly(cthylcncoxy)ethall a 1 Sod um bicarbonate.

Water Catalyst Premix:

Ammonium persullate Water Monomer Phase:

Styrene Methacrylic acid Divinylbenzeue (55% active) Glycidyllncthaerylate Neutralization Charge:

Diethanolamine Water 1 5.3 parts active. 2 Active.

EXAMPLE 15 This example illustrates the results obtained when the amountof divinylbenzene exceeds two parts per 100 parts of total monomer.

Parts by Parts by Weight per Weight 100 Parts 'lotal Monomer KettleCharge:

Ammonium salt of sulfate ester of analliylphenoxy-poly(ethyleneoxy)cthar 5 0 1. Sodium biearbonat 3. 0 Water580. 0

Catalyst Preinix:

Ammonium persullate... 2. 0

Water 20.0 Monomer Phase A:

Styrene 408 65. O

M ethacrylie acid 24 3. 8

Divinylben zene (55% active) l 24 1 2. 1 Monomer Phase B:

1 5 Styrene 128 3 Glycidyl methacrylatc... 48 7. 6 Methacrylic acid 8 1.2

1 13.2 active. 2 Active.

The procedure followed is the same as that of Ex- 0 ample 1. In thisinstance, coagulation of the latex occurred when approximatelythree-fourths of monomer phase B was added.

EXAMPLE 16 Opaeified liquid detergent composition An opacified liquiddetergent is prepared utilizing the copolymer latex obtained inExample 1. The ingredients listed below are dispersed in water to form ahomogeneous aqueous dispersion:

Percent by weight Copolymer latex 40% solids (Example 1) 1 Isopropylalcohol 5 Ammonium salt of sulfate ester of an alkylphenoxypoly(ethyleneoxy)ethanol (58% minimum activity) (Alipal CO-436) 20 Lauriediethanolamide (Superamide L-9) 3 Alkyl arylsulfonate (57.5% active)(Ultrawet 60K) 25 Water 46 Acid (dilute sulfuric) to pH 6.5 to 7.5.

This results in a milky, lotion-like detergent composition whichexhibits excellent storage stability.

EXAMPLE 17 Opacified liquid detergent composition Percent by weightCopolymer latex 40% solids (Example 1) 0.5 Ethyl alcohol 5 Ammonium saltof sulfate ester of an alkylphenoxypoly(ethyleneoxy)ethanol (58% minimumactivity) (AlipalCO-436) 8 Nonylphenoxypoly(ethyleneoxy)ethanol (IgepalCO-730) 7 Laurie diethanolamide (Snperamide L-9) 4 Alkyl aryl sulfonate(57.5% active) (Ultrawet 60K) 25 Water 50.5

Acid (dilute sulfuric) to pH 6.5 to 7.5.

This composition is an opalescent liquid which exhibits excellentstorage stability.

EXAMPLE 18 Cpacified liquid detergent composition Percent by WeightCopolymer latex, 40% solids (Example 1) 2 Ethyl alcohol 5 Sodium xylenesulfonate (Ninex 303) 15 Octyl phenoxy(polyethyleneoxy)ethanol (TritonX-102) l0 Lauric diethanolamide (Ninol AA-62 extra) 3 Alkyl arylsulfonate (57.5 active) (Ultrawet 60-K) 31 Water 34 Acid (dilutesulfuric) to pH 6.5 to 7.5.

9 EXAMPLE 19 Ten milliliters of each of the latices prepared inaccordance with Examples 1 and 13 are added to approximately 100milliliters of methanol with thorough mixing. The resultant mixture ineach instance is homogeneous and free from evidence of coagulation orprecipitation. The addition of an aqueous solution of hydrochloric acidcontaining approximately 10% by weight of HCl fails to inducecoagulation in either of the above latices.

EXAMPLE 20 Each of the latices prepared in accordance with Examples 1and 13 is allowed to evaporate at approximately 70 F. to obtain thenonvolatile matter of each. Each latex yields a powdery particulatesolid which exhibits no film-forming tendencies and which is insolublein acetone, methylethylketone, benzene, toluene and dimethylformamide.

From the foregoing examples, it may be seen that the novel copolymers ofthe present invention result in latices which are particularly useful inopacifying liquid detergents. Examples 1 through 11 demonstrate thecriticality of the monomers glycidyl methacrylate and glycidyl acrylatein the compositions herein described to provide an opacified detergentsolution displaying storage stability. Example 12 illustrates theoptimum pH range of the finished latex. Example 13 illustrates the useof a quantity of glycidyl methacrylate which is substantially less thanthat used in Example 1.

Example 14 illustrates that it is possible to prepare the latices of thepresent invention by a single monomer admixture addition rather than atwo phase technique. However, it will be observed that the resultantopacified liquid detergent employing such latex lacks that degree ofstabi ity which the same liquid detergent opacified with the latex ofExample 1 displays. This lends weight to the premise that a two-stepaddition procedure produces a latex which has enhanced opacifyingproperties.

Example 15 demonstrates the criticality of the ratio of divinylbenzeneemployed. The composition of Example 1, containing 1.3 percent by weighton a monomer basis of divinylbenzene, is a stable and effectiveopacifier latex, whereas the composition of Example 15, containing 2.1weight percent of divinylbenzene results in a coagulated, useless mass.

Examples 16, 17 and 18 demonstrate various liquid detergent compositionswhich may be opacified by means of the present latices.

Example 19 underscores the unique stability of the pres- 10 cut laticeswhich are unaffected by the presence of large volumes of methanol, asolvent generally employed as a coagulating agent for aqueous polymerlatices. Example 20 illustrates the non-film forming, cross-linkedcharacteristics of the interpolymers of the present invention.

While several particular embodiments of this invention are shown above,it will be understood, of course, that the invention is not to belimited thereto, since many modifications may be made, and it iscontemplated, therefore, by the appended claims, to cover any suchmodifications as fall within the true spirit and scope of thisinvention.

I claim:

1. A stabilized aqueous liquid opacified detergent compositionconsisting essentially of a surface active agent selected from the groupconsisting of anionic detergents, nonionic detergents and blends thereofand a cross-linked interpolymer latex, said latex being present in anamount of from 0.2 to 14 parts of polymer solids per 100 parts by weightof surface active agent, said latex comprising an interpolymer incross-linked polymerized form containing from 78 to 96 parts by weightof a monomer selected from the group consisting of styrene andmethylated styrene, from 1 to 20 parts by weight of an unsaturated acidselected from the group consisting of methacrylic acid, acrylic acid anditaconic acid, from 1 to 20 parts by weight of a monomer selected fromthe group consisting of glycidyl methacrylate and glycidyl acrylate anddivinylbenzene in an amount of up to about 2 parts per 100 of totalmonomer, the proportions of said monomers being such as to total 100parts in the aggregate.

2. A detergent composition according to claim 1 having from 3.6 to 83parts of a lower alkanol per 100 parts of the surface active agent.

3. A detergent composition according to claim 1 wherein the interpolymerlatex contains from 85 to parts styrene, from 1 to 10 parts ofmethacrylic acid, from 1 to 10 parts of glycidyl methacrylate and up to2 parts of divinylbenzene.

References Cited UNITED STATES PATENTS 3,060,124 10/1962 Ginn 252893,156,655 11/1964 Bright 25289 3,23 5,505 2/1966 Tuvell 252-89 3,282,85211/1966 Trusler et a1. 25289 LEON D. ROSDOL, Primary Examiner.

W. E. SCHULZ, Assistant Examiner.

1. A STABILIZED AQUEOUS LIQUID OPACIFIED DETERGENT COMPOSITIONCONSISTING ESSENTIALLY OF A SURFACE ACTIVE AGENT SELECTED FROM THE GROUPCONSISTING OF ANIONIC DETERGENTS, NONIONIC DETERGENTS AND BLENDS THEREOFAND A CROSS-LINKED INTERPOLYMER LATEX, SAID LATEX BEING PRESENT IN ANAMOUNT OF FROM 0.2 TO 14 PARTS OF POLYMER SOLIDS PER 100 PARTS BY WEIGHTOF SURFACE ACTIVE AGENT, SAID LATEX COMPRISING AN INTERPOLYMER INCROSS-LINKED POLYMERIZED FROM CONTAINING FROM 78 TO 96 PARTS BY WEIGHTOF A MONOMER SELECTED FROM THE GROUP CONSISTING OF STYRENE ANDMETHYLATED STYRENE, FROM 1 TO 20 PARTS BY WEIGHT OF AN UNSATURATED ACIDSELECTED FROM THE GROUP CONSISTING OF METHACRYLIC ACID, ACRYLIC ACID ANDITACONIC CID, FROM 1 TO 20 PARTS BY WEIGHT OF A MONOMER SELECTED FROMTHE GROUP CONSISTING OF GLYCIDYL METHACRYLATE AND GLYCIDYL ACRYLATE ANDDIVINYLBENZENE IN AN AMOUNT OF UP TO ABOUT 2 PARTS PER 100 OF TOTALMONOMER, THE PROPORTIONS OF SAID MONOMERS BEING SUCH AS TO TOTAL 100PARTS IIN THE AGGREGATE.